The present study introduces a mechanically robust, sealable SPME sampler for the on-site sampling and extraction of a wide range of untargeted pollutants in environmental waters. Spray-coating and dip coating methodologies were used to coat the surfaces of six stainless steel bolts with a layer of HLB/PAN particles, which served as the extractive substrate in the proposed device. In addition, this sampler was designed to withstand rough handling, long storage times, and various environmental conditions. In order to identify whether the sampler was able to stabilize extracted compounds for long periods of time, the effects of storage time and temperature were evaluated. The results of these tests showed no significant differences in the quantity and quality of the extracted chemicals following 12 days storage at room temperature, thus confirming the device's suitability for use at sampling sites that are far away from the laboratory facilities. The proposed device was also used to perform extraction and untargeted analyses of river waters in five different geographical locations. The constituent chemicals in the samplers were analyzed and determined using high-resolution HPLC-Orbitrap MS. Toxin and Toxin-Target Database was used as a reference database for toxins and environmental contaminants. Ultimately, over 80 tentative chemicals with widely varying hydrophobicities ranging within −2.43 < logP <11.9—including drugs, metabolites, wide ranges of toxins, pesticide, and insecticides—were identified in the samplers used in the different rivers. The log P values for the tentative analytes confirmed that the introduced device is suitable for the extraction and trace analysis of wide ranges of targeted and untargeted pollutants.

Microplastics (MPs) in the environment have become an issue worldwide. However, data about MPs in freshwater systems are still limited so far. This study investigated sources, fate, and seasonal and spatial distribution of MPs in the main stream Pearl River and its tributaries, as well as in the Pearl River Estuary (PRE), China. MPs were widely detected in the river water, river bed sediment, and estuarine sediment, with abundances of 0.57 ± 0.71 items L⁻¹, 685 ± 342 items kg⁻¹ dry weight (dw), and 258 ± 133 items kg⁻¹ dw, respectively. Sheet, fragmental, and fibrous polyethylene, polypropylene, and ethylene-propylene copolymers were predominant, suggesting that MPs in the Pearl River catchment be mainly derived from fragmentation of discarded plastic wastes. In addition, municipal wastewater was also an important MPs source, especially for polyethylene terephthalate (PET) fibers. Polymers of higher density, such as PET and polyvinyl alcohol were relatively more abundant in the sediment than in the river water, especially in the estuarine sediment. Upward increase of the MP abundance was observed in the sedimentary core, probably indicating increasing release of plastic wastes due to growing production and uses of plastic products. On the other hand, percentage of finer MPs increased with increasing depth. The results revealed persistence and potential downward dispersion of the fine MPs. The MPs abundance was positively related with population density and gross domestic product, demonstrating impacts of human activities and economic development on the MPs contamination. Higher MPs abundance was detected in dry season than in wet season in the river water, suggesting dilution effect of precipitation. It's estimated that 15963 tons of MPs could be released annually into the PRE from the main stream Pearl River and its tributaries.

Current understanding of how environmental aging of microplastics contributes to their ecotoxicity is low. We investigated whether incubation of microplastics in waters with different organic load and toxic potential alters the toxicity of microplastics to crustacean Daphnia magna, fish embryos Danio rerio and plant Lemna minor. Polyethylene primary microplastics; specifically microbeads from facial scrub; were subjected to 3-weeks incubation in low affected spring water, river water, effluent from the municipal wastewater treatment plant (WWTP) and municipal landfill leachate. Primary microplastics had no acute effect on D. magna mobility and D. rerio embryos development. While high organic load wastewaters; WWTP effluent and landfill leachate; showed evident toxicity for D. magna and D. rerio embryos, microplastics aged in these wastewaters had no effect. This suggests that adsorption of pollutants from wastewaters to microplastic particles was not high enough to induce acute toxicity to D. magna and D. rerio. On the contrary, primary microplastics affected the root growth of L. minor. Interestingly, aging of microplastics in low organic-load waters mitigated the toxicity of microplastics for L. minor, while microplastics aged in high-organic load waters had the same adverse effect as primary microplastics. Partly, these effects can be explained by different extent of coating on microplastics in different water samples. This study suggests that aging of microplastics in wastewaters and natural waters did not significantly enhance the toxicity to selected test species, but further studies on plants may be of interest.

Rapid development of Bohai and Yellow Sea Economic Rim has led to the concern of emerging contamination of marine environments. This study investigated the spatial distribution of antibiotic resistance genes (ARGs) in Bohai and Yellow Sea areas. A large scale sampling from Bohai Sea, Yellow Sea and the major cities along the coastline from the mouth of Yalu River to the Yangtze River was performed. The spatial distribution of target ARGs based on the absolute abundances was in the trend of river water ≈ coastal water > the Bohai Sea > the Yellow Sea, inshore > offshore and inner bay > bay mouth. The total absolute abundances of selected ARGs in the coastal waters (1.23 × 10⁴–3.94 × 10⁵ copies/mL) were about 1–4 orders of magnitude higher than those in the sea (21.1–8.00 × 10³ copies/mL). The abundances of ARGs fluctuated greatly in the Yellow Sea and the coastal areas. Sulfonamide resistance genes hold the highest abundances in the Bohai and Yellow Sea (up to 2.13 × 10³ copies/mL of sul1 and 6.23 × 10³ copies/mL of sul2), followed by tetracycline and quinolone resistance genes, while qnrA hold the highest abundances in coastal areas (up to 3.66 × 10⁵ copies/mL). The distribution coefficients of target genes between sediments and corresponding water samples were more than 1.0 in the majority of different aquatic systems. According to the principle component analysis and redundancy analysis, water samples collected from the sea clustered together while those from the coastal zone and rivers were separated. Ammonium and nitrate played important roles in the distribution and variation of ARGs. Co-occurrence network analysis revealed that the potential multi-antibiotics resistant bacteria were detected with higher abundances in the Yellow Sea than in the Bohai Sea. These observations provided a comprehensive new insight into the pollution status of ARGs in the Bohai and Yellow Sea areas.

Taihu Lake is one of the largest freshwater lakes in China and serves as an important source for drinking water. This lake is suffering from eutrophication, cyanobacterial blooms and fecal pollution, and the inflow Tiaoxi River is one of the main contributors. The goal here was to characterize the bacterial community structure of Tiaoxi River water by next-generation sequencing (NGS), paying attention to bacteria that are either fecal-associated or pathogenic, and to examine the relationship between environmental parameters and bacterial community structure. Water samples collected from 15 locations in three seasons, and fecal samples collected from different hosts and wastewater samples were used for bacterial community analysis. The phyla Proteobacteria, Actinobacteria, Bacteroidetes, and Cyanobacteria were predominant in most of the water samples tested. In fecal samples, Bacteroidetes, Firmicutes, and Proteobacteria were abundant, while wastewater samples were dominated by Proteobacteria, Bacteroidetes, Acidobacteria, and Chloroflexi. The cluster analysis and principal coordinate analysis indicated that bacterial community structure was significantly different between water, fecal and sewage samples. Shared OTUs between water samples and chicken, pig, and human fecal samples ranged from 4.5 to 9.8% indicating the presence of avian, pig and human fecal contamination in Tiaoxi River. At genus level, five bacterial genera of fecal origin and sequences of seven potential pathogens were detected in many locations and their presence was correlated well with the land use pattern. The sequencing data revealed that Faecalibacterium could be a potential target for human-associated microbial source-tracking qPCR assays. Our results suggest that pH, conductivity, and temperature were the main environmental factors in shaping the bacterial community based on redundancy analysis. Overall, NGS is a valuable tool for preliminary investigation of environmental samples to identify the potential human health risk, providing specific information about fecal and potentially pathogenic bacteria that can be followed up by specific methods.

Ammonia oxidation is the rate-limiting step in nitrification process and dominated by ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). In the present study, a highly enriched culture of AOA was obtained from urban polluted water in Shahe River, Shenzhen, China. The optimum growth conditions were identified by orthogonal analysis as 37 °C, with pH 7.0 and initial ammonia concentration of 1.0 mM. Under these conditions, the highest abundance of AOA was obtained as 4.6 × 10⁷ copies/ng DNA. Growth of AOA in polluted river water showed significant reduction in ammonia concentration in AOA-enriched cultures without antibiotics after 10 days of incubation, while synchronous increase in nitrate concentration was up to 12.7 mg/L. However, AOA-enriched by antibiotic showed insignificant changes in ammonia or nitrite concentration. This study showed that AOB play an important role in ammonia oxidation of polluted river water, and AOA alone showed insignificant changes in ammonia or nitrite concentrations. Therefore, the ammonia oxidation performance of natural water could not be improved by adding high concentration AOA bacterial liquid.

Although agricultural lands are generally assumed to correlate negatively with groundwater quality, the intricate relationship between general land cover and contaminant concentrations present in an aquifer may vary substantially; contingent upon the land type, interacting factors, and scale considered. The Upper Floridan Aquifer (UFA) is a primary source of potable water supply for the state of Florida. The Suwannee River Water Management District (SRWMD), located in northcentral Florida, relies exclusively on the UFA for water supplies. Over much of the SRWMD in the UFA is unconfined, rendering it vulnerable to contamination from surface sources. This study analyses groundwater concentrations of Nitrate-Nitrogen (NO3–N) and Potassium (K) from shallow wells across the SRWMD for assessing the effect of different land covers on groundwater quality over time. Annual potentiometric surface maps were used to delineate semicircular recharge zones of 500 m, 1000 m, and 2000 m radii upstream of sampled well stations. Proportions of agriculture, forest, and urban lands were identified for each buffer zone using USDA Cropland Data Layer. Multivariate regression models were developed to infer relationships between land cover and NO3–N and K concentrations. Results show significant associations among land cover type, water table height, and groundwater quality parameters. Specifically, we find a large proportion of agricultural cover consistently associated with larger increases in groundwater pollutant loads relative to urban or forest cover across all models, after controlling for depth to water table. Our study suggests a need for widespread adoption of cost-effective agricultural best management practices (BMPs) that could help in securing regional water supply.

The effects of fulvic acid (FA) and ions on mesophilic pathogenic bacteria survival under freeze-thaw (FT) stress in natural water and its resistant mechanisms are rarely understood. Therefore, survival patterns of Escherichia coli in river water added with various concentrations of FA or FA-ion under FT stress were studied in this work. Meanwhile, cell surface hydrophobicity (CSH), unit activities of superoxide dismutase (SOD) and catalase (CAT) were determined and Escherichia coli morphologies were observed to explore the bacterial resistant mechanisms against FT stress. The results demonstrated that FT cycles significantly reduced bacterial quantities as sampling time, i.e. freeze-thaw cycle time increased. And the biggest reducing rate was observed after the first FT cycle in every system. Ttd values, time needed to reach detection limit under FT stress decreased under FT stress as FA was added into water, while the changes of ttd values were quite complicated when FA and various ions existed together. Generally, the ttd values of FA-cation systems exceeded that of FA system except FA-Ca²⁺ systems, but it was opposite for FA-anion systems. CSH was heightened after FT cycles and reached peak value at last sampling time in every system. Mechanical constraint from extracellular ice crystals and high CSH induced bacterial aggregation, which protect inner cells of aggregation from extracellular ice crystals. And the unit activities of SOD were significantly higher than those of CAT. Unit activities of SOD and CAT in large part of tested systems increased with sampling time under FT stress, which reduced reactive oxygen species produced from repeated FT cycles. Thus, these could improve the resistance of Escherichia coli to freeze-thaw stress and promote their survival. This work explored the survival pattern and strategy of Escherichia coli in natural water under FT stress.

Excessive use of nitrogenous fertilizers and their improper management in agriculture causes nitrate contamination of surface and groundwater resources. This study was conducted along the seasonally flooded alluvial agricultural area of Indus River Basin to determine the spatial and temporal dynamics of nitrate concentrations in the groundwater along the river. Total of 112 samples were collected from shallow (30–40 ft) and deep groundwater (120–150 ft) wells at seven sites, 25 km apart from each other and covered an area of 170 km along the river, during four sampling campaigns between October 2016 to May 2017 i.e. in start, mid and end of dry season. The study period covered the whole agricultural cycle including the wet summer season with no agricultural activities under flooding and the sampling sites were always less than 2 km from the river bank. Nitrate concentrations of shallow wells were 15–54 and 20–45 mg L⁻¹ during the start and middle of dry season, respectively. However, at the end of the dry season, the highest nitrate concentrations of 35–75 mg L⁻¹ were recorded and 70% of these samples contained nitrate concentrations above the permissible limit 50 mg L⁻¹. Similar seasonal patterns of nitrate concentrations were observed in deep wells, however, δ¹⁸O data suggested lower recharge in deep well than shallow wells. The results illustrated that high nitrate concentrations in shallow wells were associated with high δ¹⁸O values indicating that the quantity of evaporated water infiltrated from the floodplain, possibly from distribution channels, along with the nitrate polluting shallow wells more than the deep wells. At the end of the dry season, nitrate concentrations exceeded the permissible limits in both shallow and deep wells, which possibly happened due to the horizontal movement of groundwater along with the nitrate mixing during vertical seepage of river water to the aquifers.

We measured the concentrations of organophosphate esters (OPEs) in some biotic samples which can serve as human foodstuffs and ambient environments including air and river water from an agricultural area of Chongqing, western China. Fish samples exhibited highest OPEs levels (960 ng/g lipid weight) among the biota, followed by chicken (676 ng/g lw), cattle (545 ng/g lw) and pigs (535 ng/g lw). Tributyl phosphate (TNBP), tris (2-methylpropyl) (TIBP) and chlorinated OPEs were the major analogs in biotic samples, which appeared similar with the patterns from river water and outdoor air, but apparently different from indoor air. To further investigate the influence of ambient environment on the distribution of OPEs in biota, we analyzed the correlation between OPEs concentrations in ambient environment and biological samples, and the results revealed that most of the samples (except for pig samples) heavily correlated with outdoor air, whereas only fish and cattle samples were strongly correlated with river water. The partitioning behaviors of OPEs among biota, air and river water were also studied through calculating the biota-water accumulation factors (BWAFs), biota-air accumulation factors (BAAFs) and air-water partitioning factor (AWPFs). Significantly linear correlations (P < 0.05) were observed between log (BWAFs) and log (KOW) values, and between log (AWPFs) and log H (Henry's law constants), nevertheless log (BAAFs) was increasing along with the log (KOA) values. The daily intake (DI) values were estimated via foodstuffs ingestion and environmental exposure. The estimated DI values of OPEs from food and ambient environments were 1.78 ng/kg-bw/day, 1.23 ng/kg-bw/day and 1.42 ng/kg-bw/day in toddlers, children and adults, respectively, which lay at the low end of the reported data and well below the reference dose (RfD).